Reaction Resin Mortar Curable by Frontal Polymerization and Method for Fixing Anchor Rods

ABSTRACT

A reaction resin mortar curable by frontal polymerization contains at least one radically polymerizable compound, at least one thiol-functionalized compound and at least one polymerization initiator, wherein the weight ratio of the at least one radically polymerizable compound and the at least one thiol-functionalized compound is in the range of 10:1 to 2:1 and wherein the polymerization initiator is selected from compounds which can be thermally activated and/or thermally released at a temperature of above 30° C. and/or ammonium persulfates which are formed in-situ from at least one organically substituted ammonium salt and at least one inorganic persulfate.

The present invention relates to a reaction resin mortar curable byfrontal polymerization having at least one radically polymerizablecompound, at least one thiol-functionalized compound and at least onepolymerization initiator, as well as to a method for fixing anchor rods,rebars or the like in solid supports using this reaction resin mortar.

Two-component reaction resin mortars based on methacrylates or epoxideresins are normally used for fixing anchor rods, rebars or similarelements in a bore hole in mineral subgrades such as concrete ormasonry. After the mixing of the constituents reacting with each other,these reaction resin mortars have a certain pot life during which theelement to be fixed can be set and reach the final strength thereofafter a further period of time has elapsed. The mentioned pot life is inthe range of a few minutes under normal conditions. Curing generallytakes place within a few minutes to hours. In each case, the two effectsare connected to each other, i.e., a longer pot life leads to a longercuring time, and these times may very depending on the environmentalconditions, namely on the temperature.

A reaction resin mortar for fixing anchorings is known from DE 39 40 309A1 which contains radically curable vinyl ester urethane as binder anddelivers fixings with excellent stability and strength.

The subject matter of DE 42 31 161 A1 is a two-component reaction resinmortar for fixing anchoring means in bore holes having a content ofcurable compounds on inorganic and organic basis and curing agents whichhas an extraordinarily favorable storability due to the content thereofof hydraulically binding and/or polycondensable compounds and curablevinyl esters, in addition to reduced shrinkage tendency, increased heatdistortion resistance, improved fire behavior, resistance to climaticconditions, higher bond strength, favorable expansion coefficients,satisfactory long-term behavior and high thermal shock resistance.

Lastly, DE 43 15 788 A1 discloses plugging resins for fixing anchorsinto fixed bodies which are present in an ampoule or cartridge andcontain, as binders, radically non-polymerizable polymers, reactivediluents having at least two (meth)acrylate groups, other reactivediluents, reactive diluents with a boiling point of 180° C., otherpolymers and a non-reactive solvent. These plugging resins allowretaining values that are common or required in the prior art, to beachieved; they are safe to handle; they contain fewer toxic componentsand the physical properties thereof can be adapted to the respectivepurpose of application.

Since it is seldom possible to work under optimal conditions even usingthese reaction resin mortars or plugging resins on construction sites,if for example a number of bore holes are first coated with thesereaction resin mortars or plugging resins and then fixing elements areintroduced after each other, different time periods result between thesetting of the curable reaction resin mortar or the plugging resin andthe introduction of the fixing elements which can lead to the prematurecuring of the reaction resin mortar or of the plugging resin such thatthe bore hole can no longer be used, which is critical, especially inthe case of high temperatures (during summer).

In order to overcome the temperature dependence of pot life and/orcuring time, the older German patent DE 100 02 367 C1 proposes areaction resin mortar curable by frontal polymerization after thermalinitiation which, in addition to a polymerizable monomer or curableresin and optionally at least one filler, contains a polymerizationinitiator for the monomer which can be thermally activated and/orthermally released at a temperature of above 30° C. and/or a curingaccelerator for the curable resin, with the type and quantity ofmonomers or resin and polymerization initiator or curing acceleratorbeing selected such that a speed of the polymerization front (frontspeed) of at least 10 cm/min results after triggering of thepolymerization. The inadequate storability is disadvantageous in thissystem.

In order to increase the storability of this system, but still provide avery reactive system, DE 101 32 336 A1 proposes using an organicallysubstituted ammonium persulfate as the polymerization initiator which ispresent only in the form of the required raw materials in separatecomponents of the reaction resin mortar and is formed only during themixing of the at least two components in-situ in the reaction resinmortar. In this regard, one component of the reaction resin mortarcontains at least one organically substituted ammonium salt, whileanother component contains at least one inorganic persulfate which formthe organically substituted ammonium persulfate in a very quickreaction, which is then available as the initiator for the radicalcuring of the reaction resin mortar.

Both the reaction resin mortar according to DE 100 02 367 C1 and thataccording to DE 101 32 336 A1 have, however, the disadvantage of beingextremely reactive systems in which high front temperatures are reached.These high temperatures lead to noticeable smoke development and foamingduring curing. Critical gases develop which are attributable to productsof decomposition. In addition, relatively strong foaming of the massesduring curing is observed with these systems. As a result of this, asolid which is not very compact is obtained which negatively affects theload values such that the application area for these reaction resinmortars is limited.

The inventors have found that by exchanging the reactive components, inparticular the reactive polymerizable compounds for less reactivecompounds, the problems could not be overcome. In fact, it was observedthat curing was insufficient and the polymerization front frequentlycollapsed and the curing thus came to a standstill before the reactionresin mortar was fully cured.

The object of the present invention now consists of providing a reactionresin mortar which cures by frontal polymerization after thermalinitiation which does not present the disadvantages described above,which in particular exhibits less smoke development and less foaming,fully cures and results in a compact mass after curing of the reactionresin mortar.

It has surprisingly now been shown that this object can be achieved bythe addition of thiol-functionalized compounds. It is thus possible toprovide a reaction resin mortar which, compared with the systems knownfrom DE 100 02 367 C1 and DE 101 32 336 A1, is less reactive, has lesssmoke development and reduced foaming, but still fully cures and leadsto a compact polymer.

The subject matter of the invention is thus a reaction resin mortarcurable by frontal polymerization, comprising at least one radicallypolymerizable compound (a), at least one thiol-functionalized compound(b) and at least one polymerization initiator (c), wherein the weightratio of the at least one radically polymerizable compound (a) and theat least one thiol-functionalized compound (b) is in the range of 10:1to 2:1 and wherein the polymerization initiator (c) is selected fromcompounds which can be thermally activated and/or thermally released ata temperature of above 30° C. and/or ammonium persulfates which areformed in-situ from at least one organically substituted ammonium saltand at least one inorganic persulfate.

The reaction resin mortar according to the invention only thensubstantially cures if the thermally-activatable and/orthermally-releasable polymerization initiator becomes active as a resultof thermal initiation, i.e. by selective or extensive heating of thesurface layer or by heating in the inside of the reaction resin mortarto a temperature of above 30° C., and triggers the polymerization of thecurable compound. It becomes possible as a result to reach practicallyany length of pot life of the mortar and to separate this completelyfrom the curing time, since the curing is started only by the thermalinitiation. In this way, it is possible to set and to adjust the elementto be fixed possibly even hours after the introduction of the reactionresin mortar into the bore hole and to carry out the curing of thereaction resin mortar within seconds to a few minutes by briefly heatingthe mortar surface.

In this regard, thermal initiation is understood as the polymerizationreaction of the reaction resin mortar being capable of being triggeredby the supply of heat at any time point, optionally after the formationthereof by the mixing of the constituents present in separatecomponents, such that a very long pot life of the reaction resin mortarresults and the curing thereof can be started at any desired time point.It is possible as a result to initially fill a large number of boreholes with the reaction resin mortar, subsequently introduce the fixingelements, adjust and then initiate the curing such that it is possibleto achieve an optimal and largely identical curing and thus largelyidentical pull-out resistance of the installed fixing elements.

Lastly, with the reaction resin mortar according to the invention it isnot only possible to carry out the frontal polymerization downwardsfollowing gravity, but also upwards in a horizontal or verticaldirection. In this way, by correspondingly setting the viscosity of thereaction resin mortar it is possible to fill bore holes openingdownwards, for example even in ceilings, with reaction resin mortar, tointroduce fixing elements and to trigger the curing by thermalinitiation.

The triggering of the polymerization of the reaction resin mortar inaccordance with the invention preferably takes place by selective orextensive heating of the surface layer with the aid of a flame, asoldering tip, a heating wire which extends either over the entirelength or a part of the length of the fixing element, a hot air fan, aflash of light/laser beam, an induction oven or the like or in-situ by achemical reaction or by heat input via a heat-conducting fixing elementinto the inside of the reaction resin mortar.

Alternatively, by corresponding selection of the constituents of thereaction resin mortar it is possible for the reaction resin mortaraccording to the invention to also spontaneously cure without thermalactivation after a certain waiting time. The inventor has found that inthe presence of a polymerization accelerator (d), polymerization of thereaction resin mortar starts even without previous thermal initiationafter a certain time which is dependent on the concentration of thepolymerization accelerator.

A compound having at least one C—C double bond is expediently used asthe radically polymerizable compound (a), which C—C double bond can beradically cured and is sufficiently stable when stored due to the absenthomopolymerization.

According to a preferred embodiment of the invention, the compoundhaving at least one reactive C—C double bond is a compound having atleast one non-aromatic C—C double bond, such as(meth)acrylate-functionalized compounds, allyl-functionalized compounds,vinyl-functionalized compounds, norbomene-functionalized compounds andunsaturated polyester compounds.

Examples of unsaturated polyester compounds can be found in the articleby M. Maik et. al. J. Macromol. Scd., Rev. Macromol. Chem. Phys. 2000,C40, 139-165 in which a classification of such compounds was made basedon the structure thereof, with five groups being mentioned: (1)orthoresins, (2) soresins, (3) bisphenol-A fumarates, (4) chlorendicsand (5) vinyl ester resins. The so-called dicyclopentadienes (DCPD)resins can also be distinguished therefrom.

More preferably, the compound having reactive carbon multiple bonds hasallyl, vinyl, (meth)acryl, fumaric acid, maleic acid, itaconic acid,crotonic acid or cinnamic acid double bond units or the compound havingreactive carbon double bonds is a Diels-Alder adduct or a norbomenederivative thereof or a derivative thereof having one other compoundwhich bears bicyclic double bonds. Exemplary compounds are vinyl esters,allyl esters, vinyl ethers, allyl ethers, vinyl amines, allyl amines,vinyl amides, esters and amides of (meth)acrylic acid, esters of fumaricacid and maleimides.

The polymerizable monomers or curable resins used according to theinvention are preferably selected from: acrylic acid, methacrylic acid,styrene, divinylbenzene, vinyl acetate, acrylamide, transition metalnitrate/acrylamide complexes; acrylates such as butyl acrylate,2-(2-ethoxyethoxy) ethyl acrylate (EOEOEA), tetrahydrofurfuryl acrylate(THFA), lauryl acrylate, phenoxyethyl acrylate, isodecyl acrylate,tridecyl acrylate, ethoxylated nonylphenol acrylate, isobornyl acrylate(IBOA), ethoxylated bisphenol A diacrylate, polyethylene glycoldiacrylate (PEGDA), alkoxylated dlacrylate, propoxylated neopentylglycol diacrylate (NPGPODA), ethoxylated neopentyl glycol dlacrylate(NPGEODA), hexane-1,6-diol dlacrylate (HDDA), tetraethylene glycoldiacrylate (TTEGDA), triethylene glycol diacrylate (TIEGDA),tripropylene glycol diacrylate (TPGDA), dipropylene glycol diacrylate(DPGDA), ditrimethylolpropane tetraacrylate (DITMPTTA),tris-(2-hydroxyethyl) isocyanurate triacrylate (THEICTA),dipentaerythritol pentaacrylate (DIPEPA), ethoxylated trimethylolpropanetriacrylate (TMPEOTA), propoxylated trimethylolpropane triacrylate(TMPPOTA), ethoxylated pentaerythritol tetraacrylate (PPTTA),propoxylated glycerol triacrylate (GPTA), pentaerythrtol tetraacrylate(PETTA), trimethylolpropane triacrylate (TMPTA) and modifiedpentaerythritol triacrylate; methacrylates such as methyl methacrylate(MMA), allyl methacrylate (AMA), tetrahydrofurfuryl methacrylate(THFMA), phenoxyethyl methacrylate, isobornyl methacrylate, triethyleneglycol dimethacrylate (TIEGDMA), ethylene glycol dimethacrylate (EGDMA),tetraethylene glycol dimethacrylate (TTEGDMA), polyethylene glycoldimethacrylate (PEGDMA), butanediol dimethacrylate (BDDMA), diethyleneglycol dimethacrylate (DEGDMA), hexanediol dimethacrylate (HDDMA),polyethylene glycol dimethacrylate (PEG600DMA), butylene glycoldimethacrylate (BGDMA), ethoxylated bisphenol A dimethacrylate,trimethylolpropane trimethacrylate (TMPTMA); and/or oligomers orprepolymers such as bisphenol A epoxy acrylate, epoxidized soybean oilacrylate, epoxy novolac acrylate oligomers, fatty acid modifiedbisphenol A epoxy acrylate, aromatic monacrylate oligomer, aliphaticdiacrylate ollgomer, tetrafunctional epoxy acrylate, amine modifiedpolyether acrylate oligomer, aliphatic urethane tracrylate, aliphaticurethane tetraacrylate, aliphatic urethane diacrylate, hexafunctionalaromatic urethane acrylate, aromatic urethane diacrylate, aromaticurethane tetraacrylate and tetrafunctional polyester acrylate.

The polymerizable monomers or curable resins can be used alone or as amixture.

The reaction resin mortar can, if necessary, contain non-reactivediluents such as lower-alkyl ketones, e.g. acetone, di-lower alkyl-loweralkanoylamides such as dimethylacetamide, lower alkyl benzenes such asxylene or toluene, phthalic acid esters or paraffins or water, inparticular a dialkyl phthalate or dialkyl adipate and/ordimethylformamide in a quantity of up to 10 wt %, in particular 5 wt %.

Any compound which has at least two thiol groups can expediently be usedas the thiol-functionalized compound (b). Any thiol group is, in thisregard, bound either directly or via a linker to a structure, and thethiol-functionalized compound of the present invention can have any widenumber of structures.

The structure can be a monomer, an oligomer or a polymer.

In some embodiments of the present invention, the structures havemonomers, oligomers or polymers with a molecular weight (mw) of 50,000g/mol or less, preferably 25,000 g/mol or less, more preferably 10,000g/mol or less, even more preferably 5,000 g/mol or less, even morepreferably 2,000 g/mol or less and most preferably 1,000 g/mol or less.

Alkane dioles, alkylene glycols, sugar, polyvalent derivatives thereofor mixtures thereof and amines such as ethylenediamine andhexamethylenediamine and thiols may be mentioned as monomers which aresuitable as structures. The following can be mentioned, by way ofexample, as oligomers or polymers which are suitable as structures:

polyalkyleneoxide, polyurethane, polyethylene vinyl acetate, polyvinylalcohol, polydiene, hydrated polydlene, alkyd, alkyd polyester,(meth)acrylic polymer, polyolefin, polyester, halogenated polyolefin,halogenated polyester, polymercaptan, as well as copolymers or mixturesthereof.

In preferred embodiments of the invention, the structure is a polyvalentalcohol or a polyvalent amine, and these may be monomers, oligomers orpolymers. The structure is more preferably a polyvalent alcohol.

In this regard, the following may be mentioned, by way of example, aspolyvalent alcohols which are suitable as structures: alkane dioles suchas butanediol, pentanedol, hexanedol, alkylene glycols such as ethyleneglycol, propylene glycol and polypropylene glycol, glycerin,2-(hydroxymethyl)propane-1,3-diol, 1,1,1-tris(hydroxymethyl)ethane,1,1,1-trimethylolpropane, di(trimethylolpropane), tricyclodecanedimethylol, 2,2,4-trimethyl-1,3-pentanediol, bisphenol A,cyclohexanedimethanol, alkoxylated and/or ethoxylated and/orpropoxylated derivatives of neopentyl glycol, tertraethylene glycolcyclohexanedimethanol, hexanediol, 2-(hydroxymethyl)propane-1,3-diol,1,1,1-tris(hydroxymethyl)ethane, 1,1,1-trimethylolpropane and castoroil, pentaerythritol, sugar, polyvalent derivatives thereof or mixturesthereof.

Any units which are suitable for binding structure and functional groupmay be used as linkers. The linker for thio-functionalized compounds ispreferably selected from the structures (I) to (XI).

1: Bond to the functional group2: Bond to the structure

The structures (I), (II), (III) and (IV) are particularly preferred asthe linkers for thiol-functionalized compounds.

The functional group for the thiol-functionalized compounds is the thiolgroup (—SH).

Particularly preferred thiol-functionalized compounds are esters ofα-thioacetic acid (2-mercaptoacetates), β-thiopropionic acid(3-mercaptopropionates) and 3-thiobutyric acid (3-mercaptobutyrates)having monoalcohols, diols, triols, tetraols, pentaols or other polyols,as well as 2-hydroxy-3-mercaptopropyl derivatives of monoalcohols,diols, triols, tetraols, pentaols or other polyols. Mixtures of alcoholsmay also be used as a basis for the thiol-functionalized compound. Inthis respect, reference is made to WO 99/51663 A1, the contents of whichare incorporated by reference into this application.

Particularly suitable examples of thiol-functionalized compounds whichmay be mentioned are: glycol-bis(2-mercaptoacetate),glycol-bis(3-mercaptopropionate), 1,2-propyleneglycol-bis(2-mercaptoacetate), 1,2-propyleneglycol-bis(3-mercaptopropionate), 1,3-propyleneglycol-bis(2-mercaptoacetate), 1,3-propyleneglycol-bis(3-mercaptopropionate),tris(hydroxymethyl)methane-tris(2-mercaptoacetate),tris(hydroxymethyl)methane-tris(3-mercaptopropionate),1,1,1-tris(hydroxymethyl)ethane-tris(2-mercaptoacetate),1,1,1-tris(hydroxymethyl)ethane-tris(3-mercaptopropionate),1,1,1-trimethylolpropane-tris(2-mercaptoacetate), ethoxylated1,1,1-trimethylolpropane-tris(2-mercaptoacetate), propoxylated1,1,1-trimethylolpropane-tris(2-mercaptoacetate),1,1,1-trimethylolpropane-tris(3-mercaptopropionate), ethoxylated1,1,1-trimethylolpropane-tris(3-mercaptopropionate), propoxylatedtrimethylolpropane-tris(3-mercaptopropionate),1,1,1-trimethylolpropane-tris(3-mercaptobutyrate),pentaerythritol-tris(2-mercaptoacetate),pentaerythritol-tetrakis(2-mercaptoacetate),pentaerythritol-tris(3-mercaptopropionate),pentaerythritol-tetrakis(3-mercaptopropionate),pentaerythritol-tris(3-mercaptobutyrate),pentaerythritol-tetrakis(3-mercaptobutyrate), Capcure® 3-800 (BASF),GPM-800 (Gabriel Performance Products), Capcure® LOF (BASF), GPM-800LO(Gabriel Performance Products), KarenzMT PE-1 (Showa Denko), 2-ethyhexylthioglycolate, isooctyl thioglycolate, di(n-butyl)thiodiglycolate,glycol-dl-3-mercaptopropionate, 1,6-hexanedithiol, ethyleneglycol-bis(2-mercaptoacetate) and tetra(ethylene glycol)dithiol.

The thiol-functionalized compound may be used alone or as a mixture oftwo or a plurality of different thiol-functionalized compounds.

According to the invention, the weight ratio of the at least oneradically polymerizable compound (a) and the at least onethiol-functionalized compound (b) Is 10:1 to 2:1, preferably 8:1 to 3:1.

The reaction resin mortar contains 10 to 98 wt %, preferably 30 to 80 wt% of a mixture of the at least one radically polymerizable compound (a)and the at least one thiol-functionalized compound (b) in theabove-mentioned weight ratio.

The mass information in wt % used here, unless otherwise indicated, isalways based on the total weight of the reaction resin mortar.

The curing of the reaction resin mortar according to the invention takesplace by radical polymerization. The polymerization initiators (c) usedfor this polymerization are compounds which, optionally in a mixturewith a catalyst or an activator as the polymerization accelerator (d),are thermally activated and/or thermally released at a temperature above30° C. such that they then cause the curing of the polymerizablecompounds.

The polymerization initiator (c) should have a half-life period t_(1/2)in the range between 1 and 200 minutes, preferably between 1 and 120minutes, at a temperature of 100° C. In chlorobenzene. The half-lifeperiod t_(1/2) is the time in which, at a given temperature, half of thepolymerization initiator (c) has decomposed. Information regarding therate of decomposition of polymerization initiators at differenttemperatures is available from the manufacturers of the polymerizationinitiators or may be determined by a person skilled in the art. Analternative way is also an estimation of the half-life period t_(1/2)from literature values for the pre-exponential factor A and theactivation energy EA which are generally also available from themanufacturers of the polymerization initiators, by means of thefollowing formula:

$t_{\frac{1}{2}} = {\frac{\ln \mspace{11mu} 2}{A} \cdot e^{\frac{- ɛ_{A}}{RT}}}$

Suitable polymerization initiators (c) are peroxides, in particulardialkyl peroxides such as di-tart-butyl peroxide, diacyl peroxides suchas dibenzoyl peroxide, hydroperoxides such as tert-butyl hydroperoxideor cumene hydroperoxide, percarbonic acid esters such as butylperbenzoate, perketals such as1,1-dl-tert-butylperoxy-3,3,5-trimethylcyclohexane, sodium persulfate,potassium persulfate, an optionally organically substituted ammoniumpersulfate (e.g. tetra-n-butylammonium persulfate) and/or an azocompound such as azobisisobutyronitrile having a half-life period oft_(1/2) in the range between 1 and 200 minutes, preferably 1 to 120minutes, at a temperature of 100° C. in chlorobenzene. Thesepolymerization initiators (c) may be used alone or as a mixture.

The term half-life period is correspondingly also used here for thecatalyzed decomposition of the polymerization initiator (c) in the givenmixture.

The polymerization initiators (c) may also be phlegmatized byencapsulation in filler materials (e.g. by microencapsulation) such thatthey become active or are released only after being heated to atemperature above 30° C. with corresponding softening or reaction of thefiller material.

Alternatively, the polymerization initiator (c) can be an ammoniumpersulfate which is formed from the corresponding raw materials onlyonce it is in-situ. At least one organically substituted ammonium saltand at least one inorganic persulfate are expediently used as rawmaterials. This results in the organically substituted ammoniumpersulfate after the mixing thereof.

Suitable organically substituted ammonium salts are: tri or inparticular tetra alkyl, aryl or aryl-alkyl ammonium salts, for example ahalide, such as for example chloride, acetate, (meth)acrylate and/orhydrogen sulfate. Particularly preferred is the use oftetrabutylammonium chloride, benzyl triethyl ammonium chloride,tetrabutylammonium hydrogen sulfate, tetradecyl dimethyl benzyl ammoniumchloride or trimethyl capryl ammonium chloride or of mixtures of thesecompounds.

Suitable inorganic persulfates are: sodium, potassium, unsubstituted orweakly substituted ammonium persulfate such as mono or dialkyl, aryland/or aryl-alkyl ammonium persulfate.

These polymerization initiators (c) may be used alone or as a mixture.

According to a further preferred embodiment of the invention, aperoxide, in particular a dialkyl peroxide such as di-tert-butylperoxide, a diacyl peroxide such as dibenzoyl peroxide, a hydroperoxidesuch as tert-butyl hydroperoxide or cumene hydroperoxide, a percarbonateacid ester such as butyl perbenzoate, a perketal such as1,1-di-tert-butylperoxy-3,3,5-trimethylcyclohexane and/or an azocompound such as azobilsobutyronitrile having a half-life period oft_(1/2) of 1 and 200 minutes, preferably 1 to 120 minutes, as definedabove [are used] in addition to ammonium persulfate, in order to improvethe curing.

The polymerization initiator (c) may be contained in a quantity of 2 to30 wt %, preferably 2 to 12 wt %, more preferably 5 to 10 wt % in thereaction resin mortar. If a mixture of polymerization initiators isused, then the total quantity of the polymerization initiators is inrange mentioned above.

In order to accelerate the polymerization, a polymerization accelerator(d) can also be added to the reaction resin mortar for the decompositionof the polymerization initiator (c). The half-life period thereof isthus shortened such that peroxides can be used which have a half-lifeperiod of more than 200 minutes at 100° C. without accelerators.

Suitable polymerization accelerators (d) are in particular amines,preferably a tertiary amine such as dimethylaniline,bis-(hydroxyethyl)-m-toluldine or similar and/or metal compounds such asa cobalt, manganese, copper, iron and/or vanadium compound.

In order to avoid a premature triggering of the polymerization by heatinput from the exterior, a catalyst for activating the polymerizationinitiator can be added to the reaction resin mortar in a secondcomponent, in encapsulated form (e.g. microencapsulation) and/orotherwise phlegmatized.

A particular example is the fixing of the polymerization accelerator (d)to a polymer which releases a metal such as cobalt, manganese, copper,iron and/or vanadium which triggers the decomposition of a peroxidepolymerization initiator above the limit temperature of at least 30° C.Correspondingly, the desired activation temperature of above 30° C. canbe set in a targeted manner by a suitable combination of polymerizationinitiators (c) and polymerization accelerators (d) or curingaccelerators, known to the person skilled in the art, havingcorresponding inhibitors.

The polymerization accelerator (d) can be contained in a quantity of 0to 1 wt %, preferably 0.1 to 0.5 wt %, in the reaction resin mortar.

In a preferred embodiment of the invention, the reaction resin mortaraccording to the invention also contains an organic and/or inorganicaggregate such as fillers and/or additives for influencing variousproperties of the masses.

As fillers, conventional fillers are used, preferably mineral ormineral-like filers such as quartz, glass, sand, quartz sand, quartzpowder, porcelain, corundum, ceramic, talcum, silicic acid (e.g.pyrogenic silicic acid), silicates, clay, titanium dioxide, chalk,barite, feldspar, basalt, aluminum hydroxide, granite or sandstone,polymer fillers such as duroplasts, hydraulically curable fillers suchas gypsum, quicklime or cement (e.g. alumina cement or Portland cement),metals such as aluminum, carbon black, also wood, mineral or organicfibers or the like, or mixtures of two or more thereof, which may beadded as powder, in granulated form or in the form of molded bodies. Thefillers may be present in any forms, for example as powder or flour oras molded bodies e.g. In cylindrical, ring, spherical, flake, bacillar,arched or crystal form or also in fiber form (fibrillar fillers), andthe corresponding elementary particles preferably have a maximumdiameter of 10 mm.

Further conceivable additives are thixotroplc agents such as optionallyorganically post-treated pyrogenic silicic acid, bentonite, alkyl andmethyl celluloses, castor oil derivatives or the like, softeners such asphthalic acid or sebacic acid esters, stabilizers, antistatic agents,thickeners, flexibilizers, curing catalysts, rheological additives,wetting agents, coloring additives such as colorants or in particularpigments, for example to dye the components differently for improvedchecking of the mixing thereof or the like or mixtures of two or aplurality thereof.

The inorganic and/or organic aggregates may be contained in the reactionresin mortar in a quantity of up to 60 wt %.

According to a preferred embodiment of the invention, the reaction resinmortar contains 10 to 98 wt % of a mixture of at least one radicallypolymerizable compound (a) and at least one thiol-functionalizedcompound (b) in a weight ratio of 10:1 to 2:1, preferably 8:1 to 3:1, 2to 12 wt % of at least one polymerization initiator (c), 0 to 1 wt % ofat least one polymerization accelerator (d), 0 to 60 wt % of at leastone inorganic and/or organic aggregate (e) and 0 to 10 wt % of at leastone solvent or diluent (f).

According to a further preferred embodiment of the invention, thereaction resin mortar contains 30 to 80 wt % of a mixture of at leastone radically polymerizable compound (a) and at least onethiol-functionalized compound (b) in a weight ratio of 10:1 to 2:1,preferably 8:1 to 3:1, 5 to 10 wt % of at least one polymerizationinitiator (c), 0 to 0.5 wt % of a polymerization accelerator (d), 20 to60 wt % of at least one inorganic and/or organic aggregate (e) and 0 to10 wt % of at least one solvent or diluent (f).

The portions of the constituents are selected such that the wt % adds upto 100 wt % respectively.

The reaction resin mortar according to the invention can be formulatedin a single or multi-component manner. In the case of thesingle-component form, the components must be selected such that curingof the reaction resin mortar takes place only after the supply of heat.With respect to improved storability, it is, however, preferred toformulate the reaction resin mortar according to the invention in amulti-component manner, in particular in two components. Similarly, themulti-component form, in particular the two-component form, is preferredfor the reaction resin mortar if an organically substituted ammoniumpersulfate is used as the polymerization initiator. In this regard, onecomponent of the reaction resin mortar contains at least one organicallysubstituted ammonium salt, while another component contains at least oneinorganic persulfate, and they form the organically substituted ammoniumpersulfate in a very quick reaction as soon as the components are mixedwith each other, said organically substituted ammonium persulfate thenbeing provided as the initiator for the radical curing of the reactionresin mortar.

A further subject matter of the invention is a method for fixing anchorrods, rebars or the like into bore holes in different mineral subgradeswhich consists of introducing the reaction resin mortar in accordancewith the invention which is described above into the bore hole.Subsequently the anchor rod, rebar or a similar fixing element isintroduced into the bore hole coated with the reaction resin mortar,whereupon the frontal polymerization is triggered by heating thereaction resin mortar to a temperature above the reaction temperature ofthe polymerization initiator and/or of the polymerization accelerator.

The mixing of the components of the reaction resin mortar may take placehere e.g. by means of a static mixer when the reaction resin mortar ispresent in two- or multi-component form. When using an ammoniumpersulfate as the polymerization initiator, the organically substitutedammonium salt which is contained in a component of the reaction resinmortar is then spontaneously reacted in-situ with the inorganicpersulfate which is contained in the at least one further component ofthe reaction resin mortar to form the corresponding organicallysubstituted ammonium persulfate such that a reaction resin mortar whichis radically polymerizable by heat action develops.

In this regard, the polymerization of the reaction resin mortar may betriggered by selective or extensive heating of the surface layer or inthe inside of the reaction resin mortar.

While it is possible to trigger the reaction resin mortar by heat inputvia a heat-conducting fixing element, according to the invention it ispreferred to carry out selective or extensive heating of the surfacelayer of the reaction resin mortar with the aid of a flame, a solderingtip, a hot air fan, a heating wire which extends either over the entirelength or a part of the length of the fixing element, a flash of light,a laser beam, an induction oven and/or in-situ with the aid of achemical reaction.

It is also possible to carry out the thermal initiation of the reactionresin mortar by heat input via a heat-conducting fixing element, whetherit is by heat conduction, by resistance heating or with the aid of ane.g. energy field radiated via the fixing element such as an electric,magnetic or electromagnetic field, for example by microwave radiation.

When carrying out the method according to the invention, the dimensionsof the bore hole and anchor rod are selected according to the prior artfor injection systems. In this regard, a quantity of the reaction resinmortar according to the invention is introduced into the prepared borehole such that the annular gap is completely filled after the setting ofthe element to be fixed. According to the invention, adjustment of theelement is possible since the reaction resin mortar is cured only afterbrief heating for a few seconds to at least 80° C.

The reaction resin mortar according to the invention is particularlysuited for chemical fixing, in particular for use in pluggingapplications in hollow bricks with a screen sleeve. It is, inparticular, thus possible here to also work with front speeds below the10 cm/min described in DE 100 02 367 C1.

In this manner, it is possible to carry out complete and especially evencuring of the reaction resin mortar without much foaming or smokedevelopment and thus to achieve a compact cured mass which leads toimproved properties.

The following examples serve to further explain the invention.

EXAMPLES

Measuring the Front Temperature as Well as the Front Speed

The measurement of the front temperature takes place in a test tube witha diameter of 6 mm. Thermoelements are provided at two measuring pointsat a suitable distance by means of which the change of the temperaturecan be measured. The reaction resin mortar to be examined is introducedinto the test tube at room temperature (23° C.). The polymerization ofthe reaction resin mortar is triggered by ignition by means of asoldering iron at approximately 200° C. at one point on the mortarsurface. The temperature can be determined at the measuring points. Thefront speed can be calculated from the quotient of the distance betweenthe two measuring points and the time difference between the temperaturepeaks.

The open time is the time period within which the finished mixedreaction resin mortar can be processed at room temperature. In thisregard, no open time can be indicated for mortar masses which do notspontaneously cure.

Measuring the Failure Loads

In order to determine the failure loads of the cured mass, holes with adiameter of 16 mm and a depth of 85 mm are drilled in hollow bricksanalogous to EN 791-1, but with a compressive strength of approximately35 MPa, and HIlti HIT-SC 16*85 screen sleeves (1) are used, as isschematically depicted in FIG. 1, with an insertion end (2) and an openend (3) to fill the screen sleeve (1) with reaction resin mortar and toaccommodate the anchor rods, which are lightly wrapped with a resistancewire (resistance value approximately 10 Ohm) (4) according to FIG. 1.After filling the screen sleeves (1) with the reaction resin mortar,threaded anchor rods of the dimension M10 are set and the curing isstarted by briefly applying a voltage of approx. 12 V via the heatingwire (4). The average failure loads are determined by centricallypulling out the threaded anchor rods. Three threaded anchor rods areplugged in, in each case and the load values thereof are determinedafter two hours of curing.

The failure loads (kN) determined here are given as mean values in Table1 below.

Examples 1 to 8

Reaction resin mortars are manufactured using the constituents indicatedin Table 1 below and the front temperatures and the front speeds aredetermined for the polymerization as well as the failure loads, asdescribed above.

It is clear from the results that the front temperatures could be inpart notably reduced by using the thiol-functionalized compounds, inparticular for examples 1 to 8. This leads to reduced foaming andimproved curing of the masses. Accordingly, higher failure loads couldbe achieved with the reaction resin mortars according to the inventionthan with the reaction resin mortars according to the comparativeexamples. The results also show that with the compositions according tothe invention it is no longer essential for the polymerization front tohave to progress at a determined speed in order to achieve sufficientcuring of the masses, as in the masses according to DE 100 02 367 C1. Itcould thus be shown that with the reaction resin mortars according tothe invention good curing is no longer dependent on the front speed.

TABLE 1 Compositions of the reaction resin mortar - Results of thetemperature measurement of the polymerization front ComparativeComparative example 1 example 2 Example 1 Example 2 Example 3 Example 4Example 5 Example 6 Example 7 Example 8 TMPTMA¹ 10 g 8.9 g 8 g 6.7 g 16g  8.9 g 13.3 g  CN 975² 10 g  20 g 8.9 g 8 g 6.7 g 2 g 16.5 g  13.3TMP(EO)TA³ 8.9 g PETMP⁴ 2.2 g 4 g 6.7 g 2 g 2.2 g 3.3 g 6.7 TMPMP⁵ 6.7 gPerkadox 20S⁶  4 g   4 g 4 g   4 g   4 g TBAPS⁷ 1.4 g   Butylperbenzoate 1.5 g TMCH⁹ 1.6 g 1.6 g 1.6 g Octa-Soligen Mn⁸ 0.2 gPyrogenic silicic acid 1.2 g  1.2 g 1.2 g 1.2 g   1.2 g 2 g   2 g 1.2 g1.2 g 1.2 g Ene:Thiol — — 8:1 4:1 2:1 9:1 8:1 2:1 5:1 2:1 Half-lifeperiod t_(1/2) at 23 109 23 23 23 56 23 4 109 109 100° C. Temperature [°C.] 223 240 185 165 133 112 125 215 210 195 Open time [min] n/a n/a n/a120 60 n/a n/a 8 75 45 Front speed [cm/min] 1.3 15 2 1.6 1.4 11 1.7 2.98 4 Failure load [kN] M10 * 80 mm 0.5 0.6 1.1 1.9 1.3 2.3 1.2 6.9 1.12.4 ¹Trimethylolpropane trimethacrylate ²Hexafunctional aromaticurethane acrylate oligomer (Sartomer) ³9-fold ethoxylatedtrimethylolpropane triacrylate ⁴Pentaerythritol tetra(3-mercaptopropionate) ⁵Trimethylolpropane tris(3-mercaptopropionate)⁶20% dibenzoyl peroxide on gypsum basis (AkzoNobel Polymer Chemicals)⁷Tetrabutylammonium peroxodisulfate ⁸10% manganese octanoate (OMGBorchers) ⁹1,1-di-(tert-butylperoxy)-3,3,5-trimethylcyclohexane

1-13. (canceled) 14: A method for fixing anchor rods, or rebars in boreholes of different subgrades, said method comprising: introducing areaction resin mortar into the bore hole, inserting the anchor rod, orthe rebar into the bore hole, and triggering the frontal polymerizationby heating the reaction resin mortar to a temperature above the reactiontemperature of the polymerization initiator or of the polymerizationaccelerator, wherein the reaction resin mortar is curable by frontalpolymerization and comprises (a) at least one radically polymerizablecompound. (b) at least one thiol-functionalized compound, and (c) atleast one polymerization initiator, wherein a weight ratio of the atleast one radically polymerizable compound (a) and the least onethiol-functionalized compound (b) is in the range of 10:1 to 2:1, andwherein the polymerization initiator (c) is selected from compoundswhich can be thermally released at a temperature of 30° C. and/orammonium persulfates which are formed in-situ from at least oneorganically substituted ammonium salt and at least one inorganicpersulfate. 15: The method according to claim 14, which is suitable forfixing anchor rods, or rebars in hollow subgrades. 16: The methodaccording to claim 14, wherein the polymerization of the reaction resinmortar is triggered by selective or extensive heating of the surfacelayer or in the inside the mortar mass. 17: The method according toclaim 14, wherein the polymerization of the reaction resin mortar istriggered by the supply of heat via the anchor rod or rebar. 18: Themethod according to claim 16, wherein the selective or extensive heatingtakes place with the aid of a flame, a soldering tip, a heating wire, ahot air fan, an induction oven, a flash of light, a laser beam and/orin-situ by a chemical reaction.
 19. The method according to claim 14,wherein the reaction resin mortar comprises 10 to 98 wt % of a mixtureof the at least one radically polymerizable compound (a) and the atleast one thiol-functionalized compound (b).
 20. The method according toclaim 14, wherein the reaction resin mortar comprises 2 to 30 wt % ofthe polymerization initiator (c).
 21. The method according to claim 14,wherein the reaction resin mortar comprises an ammonium persulfate asthe polymerization initiator (c), wherein the at least one organicallysubstituted ammonium salt and the at least one organic persulfate arepresent separately in a reaction inhibiting manner such that theorganically substituted ammonium persulfate is formed only after themixing thereof.
 22. The method according to claim 21, wherein thereaction resin mortar comprises, as an organically substituted ammoniumsalt, a tri or tetra alkyl, aryl or aryl-alkyl ammonium halide, acetate,(hydrogen)carbonate, (hydrogen)phosphate, (hydrogen)sulfate,(meth)acrylate or mixtures of these compounds.
 23. The method accordingto claim 21, wherein the reaction resin mortar comprises, as aninorganic persulfate, ammonium, potassium or sodium persulfate ormixtures of these compounds.
 24. The method according to claim 14,wherein the reaction resin mortar comprises, as the polymerizationinitiator (c), a peroxide and/or an azo compound, which, optionally inthe presence of a polymerization accelerator (d), each have a half-lifeperiod t½ in the range between 1 and 200 minutes at a temperature of100° C. in chlorobenzene.
 25. The method according to claim 14, whereinthe reaction resin mortar further comprises a polymerization accelerator(d).
 26. The method according to claim 14, wherein the reaction resinmortar further comprises inorganic and/or organic aggregates.
 27. Themethod according to claim 26, wherein the aggregate is selected fromfillers and/or additives.
 28. The method according to claim 27, whereinthe aggregate is contained in the reaction resin mortar in a quantity ofup to 60 wt %.
 29. The method according to claim 25, wherein thepolymerization accelerator (d) is selected from amines, sulfides,thiourea or mercaptans and/or metal compounds.
 30. The method accordingto claim 25, wherein the polymerization accelerator (d) is contained inthe reaction resin mortar in a quantity of 0.01 to 1 wt %.
 31. Themethod according to claim 14, wherein the at least onethiol-functionalized compound (b) contains at least two thiol groups.